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WO2019198622A1 - Composition de polissage - Google Patents

Composition de polissage Download PDF

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Publication number
WO2019198622A1
WO2019198622A1 PCT/JP2019/015060 JP2019015060W WO2019198622A1 WO 2019198622 A1 WO2019198622 A1 WO 2019198622A1 JP 2019015060 W JP2019015060 W JP 2019015060W WO 2019198622 A1 WO2019198622 A1 WO 2019198622A1
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WO
WIPO (PCT)
Prior art keywords
polishing
ceria
polishing composition
cellulose
particles
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2019/015060
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English (en)
Japanese (ja)
Inventor
小松　通郎
西田　広泰
祐二 俵迫
中山　和洋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
JGC Catalysts and Chemicals Ltd
Original Assignee
JGC Catalysts and Chemicals Ltd
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Publication date
Application filed by JGC Catalysts and Chemicals Ltd filed Critical JGC Catalysts and Chemicals Ltd
Priority to JP2020513234A priority Critical patent/JP7307053B2/ja
Publication of WO2019198622A1 publication Critical patent/WO2019198622A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B37/00—Lapping machines or devices; Accessories
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/146—After-treatment of sols
    • C01B33/149—Coating
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/18—Preparation of finely divided silica neither in sol nor in gel form; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09G—POLISHING COMPOSITIONS; SKI WAXES
    • C09G1/00—Polishing compositions
    • C09G1/02—Polishing compositions containing abrasives or grinding agents
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/14—Anti-slip materials; Abrasives
    • H10P52/00—

Definitions

  • the present invention is capable of polishing a substrate at a high speed in polishing a substrate or the like on which a silica-based film is formed, and having few polishing scratches on the substrate, and also having a small amount of foreign matter remaining on the substrate, for example, abrasive grains or organic matter remaining. Relates to the composition.
  • the surface state affects the semiconductor characteristics, and therefore, it is required to polish the surfaces and end faces of these components with extremely high accuracy.
  • a polishing method for such a member after performing a relatively rough primary polishing process, a precise secondary polishing process is performed, so that a highly accurate surface with few scratches such as a smooth surface or scratches is obtained. A method of obtaining a surface is used.
  • abrasive used for such secondary polishing for example, colloidal silica obtained by growing silica particles by pyrolyzing silicon tetrachloride and adjusting the pH with an alkaline solution not containing an alkali metal such as ammonia.
  • System abrasives are known.
  • such an abrasive has a problem that the polishing rate of the inorganic insulating film is not sufficient and the polishing rate is slow.
  • cerium oxide particles have a low polishing rate compared to silica particles and alumina particles, although they are low in hardness. Further, cerium oxide is useful for finishing mirror polishing because it hardly causes scratches on the polished surface. Furthermore, cerium oxide has chemically active properties, as is known as a strong oxidant. Taking advantage of this advantage, application to a chemical mechanical polishing agent for insulating films is useful. However, when applied to polishing primary and secondary inorganic insulating films for LSIs of 32 nm node and beyond, there is a problem that the primary particle size is large and thus the surface of the insulating film is damaged by polishing.
  • the median particle diameter obtained by firing and pulverizing cerium carbonate hydrate is 100 to 1500 nm, and is composed of two or more crystallites.
  • An abrasive containing cerium oxide particles having a boundary is disclosed.
  • an aqueous solution of cerium nitrate and a base are stirred and mixed at a quantitative ratio of pH 5 to 10, followed by rapid heating to 70 to 100 ° C. and aging at that temperature.
  • Cerium oxide particles composed of a single crystal of cerium oxide having a particle diameter of 10 to 80 nm are disclosed, and the surface of glass, quartz, silicon, tungsten, electroless nickel / phosphorous plating, cemented carbide, etc. is flattened with the cerium oxide particles.
  • polishing materials that is, the field of optical elements such as lenses, the field of electronic materials constituting display elements such as cathode ray tubes and liquid crystals, the field of parts constituting electronic device manufacturing equipment such as photomasks, information on hard disks, etc. It is described that it is used in the field of recording parts, flattening processing used during the processing of silicon wafers and integrated circuits, that is, in the field of semiconductor manufacturing. .
  • Patent Document 3 includes ceria-based fine particles having an average particle diameter of 50 to 300 nm in which child particles mainly containing crystalline ceria are bonded to the surface of mother particles mainly containing amorphous silica.
  • a ceria-based composite fine particle dispersion is disclosed.
  • the ceria-based composite fine particle dispersion can be polished at a high speed even if it is a Si wafer or a difficult-to-work material, and at the same time, high surface accuracy (low scratch, etc.) can be achieved.
  • the silica-based composite particles described in Patent Document 3 have a large particle size, the polishing rate is high, and since the child particles with a small particle size are in contact with the polishing surface, polishing scratches hardly occur, and the child Since the particles are bonded to the mother particles, they are difficult to remain on the substrate. And since it is spherical, the fluidity of the abrasive grains is good and the polishing stability is high. However, there is a need for a polishing composition having a higher polishing rate, fewer polishing flaws, and less abrasive grains remaining on the substrate.
  • cerium oxide has a large chemical polishing action
  • the chemical polishing action is increased and the polishing rate is improved.
  • they are easily detached from the mother particles, and the detached cerium oxide particles are likely to remain on the substrate, leading to an increase in defects and a decrease in yield.
  • a fluorine compound or amine compound that is highly reactive with silica is used to increase the chemical polishing action, the polishing rate is improved, but electrical problems due to residual contamination such as erosion or resist contamination tend to occur.
  • An object of the present invention is to increase the mechanical friction effect using abrasive grains that are less likely to cause defects, whereby a substrate on which a silica coating or the like is formed can be polished at a high speed, and at the same time a high surface such as low scratches.
  • An object of the present invention is to provide a polishing composition that can achieve accuracy and is suitable for a semiconductor substrate.
  • the inventors of the present invention focused on the relationship between the polishing pad and the abrasive grains while intensively studying a polishing composition such as a substrate on which a silica-based film was formed. That is, the surface of the polishing pad is usually uneven by a dresser so that the polishing composition reaches the pad surface portion efficiently and uniformly. It was thought that this relationship had an effect on polishing efficiency. In other words, it was thought that the polishing efficiency was improved by improving the friction effect. However, if the abrasive concentration and / or the polishing pressure can be increased in relation to the texture of the surface of the polishing pad, the polishing efficiency can be improved. However, increasing the abrasive concentration increases polishing flaws and causes polishing.
  • microfibril cellulose having a phosphate group
  • microfibril cellulose having a phosphate group phosphate esterified microfibril cellulose
  • microfibril cellulose having a phosphate group phosphate esterified microfibril cellulose
  • II microfibril cellulose
  • the present inventors presume the mechanism of the remarkable improvement of the polishing characteristics of the present invention as follows.
  • Abrasive grains are trapped in (phosphorylated) microfibril cellulose by the affinity between the abrasive grain surface and phosphate groups of phosphorylated microfibril cellulose, etc., or phosphoric acid compounds.
  • the pressing force from the polishing pad is effectively transmitted to the abrasive grains, the contact efficiency of the abrasive grains to the substrate is increased, the friction is increased, and as a result, the polishing rate is improved.
  • the polishing efficiency is improved. Get higher.
  • Polishing composition (dispersion) containing microfibril cellulose has a high viscosity due to entanglement of fibers, but when shearing force is applied, the entanglement is unwound and the viscosity is extremely high. descend. Although unevenness is formed on the surface of the polishing pad, a shearing force is applied to this dispersion at a location where the distance between the polishing pad and the substrate is narrow (for example, the polishing pad is a convex portion and the substrate is a convex portion).
  • the slurry (polishing composition) flows at a high speed through a narrow gap between the polishing pad and the substrate, and the polishing speed is improved.
  • Microfibril cellulose has a fiber length on the order of ⁇ m and a fiber diameter on the order of nm, so that it flows so as to sweep the substrate and adheres to the coarse particles remaining on the substrate. It has a cleaning effect (hereinafter also referred to as scavenger effect) that removes easily abrasive grains (child particles), and other residues such as polishing scraps and organic matter.
  • the residue on the substrate can be more efficiently removed in combination with the affinity by the functional group of the phosphate esterified microfibril cellulose or the phosphate compound. As a result, the residence time of the residue can be shortened, so that the rate of occurrence of polishing flaws can be reduced, and therefore polishing flaws on the substrate can be reduced.
  • the polishing composition containing microfibril cellulose does not cause coarsening of the abrasive grains in the tank and in the line due to the effect of preventing sedimentation and aggregation of the abrasive grains. That is, it has the effect of suppressing the occurrence of scratches and the like due to the dispersion effect.
  • a polishing composition comprising at least one component selected from the following I) and II), abrasive grains, and a dispersion medium.
  • the phosphate esterified microfibril cellulose is an ammonium phosphate esterified microfibril cellulose in which a hydrogen atom of a phosphate group is substituted with ammonium.
  • the phosphate esterified microfibril cellulose has a phosphate group-derived acid group content of 0.1 to 16.8 mmol / g, according to [1] or [2] Polishing composition.
  • the phosphate esterified microfibril cellulose has a content of strong acid groups derived from phosphate groups of 0.1 to 8.4 mmol / g, and any one of [1] to [3] The polishing composition according to 1.
  • the phosphate esterified microfibril cellulose has a number average fiber diameter of 1 to 100 nm, a number average fiber length of 0.01 to 300 ⁇ m, and a ratio of the number average fiber length to the number average fiber diameter (number average fiber length /
  • the microfibril cellulose has a number average fiber diameter of 1 to 100 nm, a number average fiber length of 0.01 to 300 ⁇ m, and a ratio of the number average fiber length to the number average fiber diameter (number average fiber length / number average fiber diameter). ) Is a cellulose fiber of 10 to 3000.
  • the abrasive grains include a mother particle mainly composed of amorphous silica, and a silica layer mainly composed of amorphous silica provided on the surface of the mother particle. Crystals are formed on the silica layer.
  • the ceria-based composite fine particles have an average particle diameter of 50 to 350 nm, a mass ratio of silica to ceria (M SiO2 : M CeO2 ) of 100: 11 to 316, and an average crystallite diameter of ceria.
  • a substrate on which a film is formed can be polished at high speed, and at the same time, high surface accuracy such as low scratch can be achieved.
  • (A) is an SEM image of the ceria-based composite fine particles obtained in Preparation Examples 1-1 and 2-1, and (b) and (c) are obtained in Preparation Examples 1-1 and 2-1. It is a TEM image of ceria system fine particles. 3 is an X-ray diffraction pattern of ceria-based composite fine particles obtained in Preparation Examples 1-1 and 2-1.
  • the polishing composition of the present invention is characterized by comprising at least one component selected from the following I) and II), abrasive grains, and a dispersion medium.
  • the polishing composition of the present invention can be used as a polishing composition for a substrate (including a semiconductor substrate or other substrate) on which a silica-based coating, a copper-based coating, a tungsten-based coating, or the like is formed. It can be suitably used as a polishing composition for a formed substrate and a substrate on which a copper-based coating is formed. More specifically, it is suitable for planarization of a semiconductor substrate on which a SiO 2 insulating film (CVD film formation, thermal oxide film, low dielectric constant film, etc.) is formed, and Cu-CMP in which a copper film is formed. Can be used.
  • a SiO 2 insulating film CVD film formation, thermal oxide film, low dielectric constant film, etc.
  • examples of the polishing target of the polishing composition of the present invention include a substrate on which a silicon nitride film, a tantalum film, a tantalum nitride film, etc. are formed, sapphire, GaN, SiC, diamond, GaAs, aluminum nitride, LiTaO 3 , LiNbO 3.
  • the hard-polishing substrate which consists of can be illustrated.
  • the composition of the present invention is preferably used for rough polishing before the final polishing.
  • primary polishing is performed using the polishing composition of the present invention
  • secondary polishing is performed using a second polishing composition containing abrasive grains and a dispersion medium.
  • the abrasive grains used in the primary polishing process and the abrasive grains used in the secondary polishing process may use the same fine particles or different fine particles.
  • abrasive grains applicable to the second polishing composition that requires more stringent conditions are preferable from the viewpoint of reducing defects.
  • the first polishing composition can be selected from abrasive grains that emphasize the polishing rate.
  • the supply of the polishing composition of the present invention is preferably a dropping method.
  • the dropping is not limited to intermittent droplet supply, but includes continuous supply that does not become droplets, but does not include spraying.
  • Spraying is preferably a dripping method because coarse aggregates may be formed after drying.
  • polishing composition of the present invention by using at least one component selected from I) phosphate esterified microfibril cellulose and II) microfibril cellulose and phosphate compound together with the abrasive grains, (a) fluidity (B) Low defects (scratch generation suppression, etc.) due to improved fluidity and dispersibility, (c) (phosphate esterification) microfibril cellulose fiber shape adhesion Low abrasive grain residue due to cleaning effect (scavenger effect) of abrasive grains, polishing scraps, etc., and low adhesion, (d) (phosphate esterification) Storage stability and redispersibility due to abrasive dispersion effect of microfibril cellulose And segregation suppression in the polishing pad, (e) improvement of circuit board flatness based on non-Preston effect (pseudoplastic flow), (f) polishing pad The service life of the polishing pad can be prolonged due to the fact that particles do not easily remain in the polishing
  • the abrasive grains are, for example, fine particles having an average particle diameter of about 10 to 500 nm, and the material can be appropriately selected in consideration of the material of the substrate to be polished and the compatibility with (phosphorylated) microfibril cellulose. it can.
  • the abrasive material preferably contains at least one of cerium oxide (ceria), chromium oxide, silica, aluminum oxide, titanium oxide, and iron oxide. That is, it is preferable that the abrasive grains are composed of these one kind of oxide or composite oxide. Among these, fine particles containing ceria (ceria-based fine particles) are preferable.
  • the number of coarse particles of 0.51 ⁇ m or more is preferably 100 million particles / mL or less, and 700,000 particles / mL or less in terms of dryness of the abrasive particles. More preferably. As a result, defects such as scratches can be reduced.
  • the method for measuring coarse particles is to adjust the dilution of the sample to 0.1% by mass with pure water as an oxide (for example, the sum of CeO 2 and silica in the case of ceria-based fine particles), collect 5 ml, and this is conventionally known.
  • Into a coarse particle number measuring apparatus Then, the number of coarse particles of 0.51 ⁇ m or more is obtained. This measurement is performed three times to obtain a simple average value, which is multiplied by 1000 to obtain a value of the number of coarse particles of 0.51 ⁇ m or more.
  • the content of abrasive grains in the polishing composition of the present invention is preferably 0.1 to 10% by mass, and more preferably 0.2 to 3% by mass.
  • concentration is lower than 0.1% by mass, it is effective for polishing scratches and the like, but the polishing rate decreases.
  • concentration is higher than 10% by mass, the redispersibility of the sedimented slurry is poor, and the polishing scratches (defects) tend to increase.
  • the content of each element of Na, Ag, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, Al, and Zr is preferably 10 ppm or less, and preferably 5 ppm or less. More preferred is 1 ppm or less.
  • the content of each element is within this range, metal contamination can be prevented and the stability of the abrasive grains is further increased. Therefore, when applied to the polishing composition, the occurrence of scratches is further suppressed.
  • U, Th, Cl, NO 3, SO 4 and the content of F is preferably not 1ppm or less.
  • the content of each element is a value obtained by the same method as that used for the mother particles of the ceria-silica composite oxide fine particles (1) described later.
  • ceria-based fine particles are oxide fine particles containing crystalline cerium oxide (ceria), the form thereof is not particularly limited.
  • examples of such ceria-based fine particles include fine particles composed of substantially crystalline cerium oxide (ceria) such as colloidal ceria (ceria fine particles) and calcined ceria fine particles, and ceria-silica composite oxide fine particles. Can do.
  • the fine particles composed of substantially crystalline cerium oxide (ceria) calcined ceria obtained by firing and crushing cerium salts such as cerium carbonate, cerium hydroxide, colloidal ceria, etc., and cerium Examples thereof include colloidal ceria synthesized by a reaction between a salt and an alkali source.
  • the average particle size of the fine particles made of substantially crystalline cerium oxide (ceria) is preferably 10 to 500 nm.
  • the crystallite diameter of ceria is preferably 10 to 300 nm.
  • the ceria-silica composite oxide fine particles are oxide fine particles containing at least crystalline ceria and silica, and may contain other metals such as lanthanum, zirconium, aluminum, and iron. In addition, silicon, lanthanum, zirconium and other elements may be dissolved in ceria.
  • Specific examples of the ceria-silica composite oxide fine particles include the following forms. 1) What has a silica layer in the outer layer of silica fine particles, and ceria fine particles are dispersed in the silica layer (hereinafter referred to as ceria-silica composite oxide fine particles (1)). 2) Ceria fine particles buried in silica fine particles. 3) Ceria fine particles supported on the surface of silica fine particles. 4) A product having a ceria layer as an outer layer of silica fine particles. 5) A solution in which a silica component and a ceria component are dissolved.
  • the average crystallite diameter of the ceria fine particles is preferably 10 to 50 nm.
  • the method for measuring the child particles of the ceria-silica composite oxide fine particles (1) described later can be used.
  • the average particle size of the ceria-silica composite oxide fine particles is preferably 50 to 350 nm, and more preferably 70 to 260 nm.
  • the average particle diameter is measured by an image analysis method using an electron microscope. Specifically, it refers to a value obtained by the same method as that used for the mother particles of the ceria-silica composite oxide fine particles (1) described later.
  • the ceria-based fine particles may be fine particles exemplified above and may be crystalline ceria fine particles, but ceria-silica composite oxide fine particles are particularly preferable, and ceria-silica composite oxide fine particles (1) are particularly preferable.
  • the ceria-silica composite oxide fine particles (1) are excellent in stability because the outermost layer is covered with a silica layer and the surface has a negative potential. The outermost silica layer is easily dropped or peeled off by polishing pressure or frictional force, so that crystalline ceria is easily exposed and the ceria polishing effect is exhibited in the presence of silica.
  • the crystalline ceria is formed on the silica mother particles, and the size of the mother particles is the same as that of calcined ceria or colloidal ceria.
  • the silica mother particles as a core, the particle size distribution becomes sharp, so that the occurrence of defects can be suppressed.
  • the ceria-silica composite oxide fine particles (1) will be described in detail.
  • the ceria-silica composite oxide fine particles (1) have a mother particle mainly composed of amorphous silica, and a silica layer mainly composed of amorphous silica provided on the surface of the mother particle, Child particles mainly composed of crystalline ceria are dispersed in the silica layer.
  • the ceria-silica composite oxide fine particles (1) can be produced, for example, by the method described in WO2016-159167.
  • the mother particles in the ceria-silica composite oxide fine particles (1) are particles mainly composed of amorphous silica.
  • Silica has a spherical shape with a uniform particle size, and it is easy to obtain one with uniform particle size variations.
  • the silica contained in the mother particles is amorphous means that, for example, the mother particles are pulverized using a mortar, and an X-ray diffraction pattern is obtained using a conventionally known X-ray diffractometer (for example, RINT1400, manufactured by Rigaku Corporation). Can be confirmed.
  • Amorphous silica does not show the peak of crystalline silica like Cristobalite.
  • the “main component” means that the content is 90% by mass or more. That is, in the mother particles, the content of amorphous silica is 90% by mass or more. This content is preferably 95% by mass or more, more preferably 98% by mass or more, more preferably 99.5% by mass or more, and further comprising substantially amorphous silica. preferable.
  • “substantially” means that impurities and damages inevitably included from the raw materials and the manufacturing process can be included, but the other is not included. In the following description of the present invention, “main component” and “substantially” are used in this sense.
  • the mother particles are mainly composed of amorphous silica and may contain other materials such as crystalline silica and impurity elements.
  • the content of each element of Na, Ag, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, and Al in the mother particle is preferably 10 ppm or less, and preferably 5 ppm or less. Is more preferable, and it is still more preferable that it is 1 ppm or less.
  • the content of each element of SO 4 and F is preferably 1ppm or less.
  • the child particles are in relation to the mother particles. And bond tightly.
  • each element in the mother particle is measured by the following method. First, about 1 g of silica sol sample (solid content 20% by mass) containing silica fine particles (mother particles) is collected in a platinum dish. Add 3 ml of phosphoric acid, 5 ml of nitric acid and 10 ml of hydrofluoric acid and heat on a sand bath. Once dry, add a small amount of water and 50 ml of nitric acid to dissolve and place in a 100 ml volumetric flask and add water to make 100 ml. In this solution, Na and K are measured by an atomic absorption spectrometer (for example, Z-2310, manufactured by Hitachi, Ltd.).
  • an atomic absorption spectrometer for example, Z-2310, manufactured by Hitachi, Ltd.
  • the operation of collecting 10 ml of the liquid separation from the solution in 100 ml into the 20 ml volumetric flask is repeated 5 times to obtain 5 10 ml of the liquid separation.
  • Ag, Ca, Cr, Cu, Fe, Mg, Ni, Ti, Zn, U, and Th are measured by a standard addition method with an ICP plasma emission spectrometer (for example, SPS5520, manufactured by SII).
  • an ICP plasma emission spectrometer for example, SPS5520, manufactured by SII.
  • a blank is also measured by the same method, and the blank is subtracted and adjusted to obtain measured values for each element.
  • the content (content) of the components of Na, Ag, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, U, and Th in the present invention is as described above. It shall mean the value obtained by measuring by the method.
  • the average particle diameter of the mother particles is preferably 30 to 350 nm, and more preferably 60 to 300 nm.
  • the average particle diameter of the base particles is in the above range, scratches are reduced and the dispersibility is good when the dispersion of the present invention is used as an abrasive. If the average particle diameter of the mother particles is too small, the polishing rate is insufficient or problems with the stability of the particles occur, which is not preferable. If the average particle size is too large, scratches tend to occur.
  • the average particle diameter of the mother particles is measured by an image analysis method using an electron microscope. Specifically, nitric acid is first added to the ceria-silica composite oxide fine particles (1) to dissolve the child particles. Further, after adding pure water and stirring, the mother particles are settled by centrifugation, and the supernatant is removed. By repeating this, it is heated and dried on a sand bath to obtain only mother particles. Next, in a photographic projection view obtained by taking a photograph of the mother particles at a magnification of 300,000 times (or 500,000 times) with a transmission electron microscope, the maximum diameter of the particles is taken as the major axis, and the length is measured, The value is defined as the major axis (DL).
  • a point that bisects the major axis on the major axis is determined, two points where a straight line perpendicular to the major axis intersects the outer edge of the particle are obtained, and the distance between the two points is measured to obtain a minor axis (DS). Then, a geometric average value of the major axis (DL) and the minor axis (DS) is obtained, and this is used as the average particle diameter of the mother particles. In this way, the average particle diameter is measured for 50 or more particles, and the number average value thereof is calculated. The value thus obtained is taken as the average particle diameter of the mother particles of the present invention.
  • the shape of the mother particle is not particularly limited, and for example, spherical, bowl-shaped, bowl-shaped, short fiber-like, tetrahedral (triangular pyramid), hexahedral, octahedral, indeterminate, and bowl-shaped protrusions on the surface It may be a saccharide, a confetti-like one, or a porous one, but a spherical one is preferred.
  • the spherical shape means that the ratio of the number of particles having a minor axis / major axis ratio of 0.8 or less is 10% or less.
  • the mother particles preferably have a minor diameter / major diameter ratio of 0.8 or less and a number ratio of particles of 5% or less, and more preferably 0%.
  • the minor axis / major axis ratio is measured by the same method as the measuring method (image analysis method) of the minor axis / major axis ratio of the ceria-silica composite oxide fine particles (1) described later.
  • the child particles mainly composed of crystalline ceria are dispersed in the silica layer provided on the surface of the base particles as described above. That is, the child particles are bonded to the surface of the mother particle in a dispersed state in the silica layer.
  • Crystalline ceria can be confirmed as follows.
  • ceria-silica composite oxide fine particles (1) are pulverized using a mortar and an X-ray diffraction pattern is obtained by, for example, a conventionally known X-ray diffractometer (for example, RINT1400, manufactured by Rigaku Corporation), ceria crystals are obtained. Phase is detected. Particularly preferably, only the crystalline phase of ceria is detected. Ceriaite is an example of the ceria crystal phase.
  • the child particles are mainly composed of crystalline ceria (crystalline Ce oxide), and may contain other elements, for example, elements other than cerium.
  • crystalline ceria crystalline Ce oxide
  • the definition of “principal component” is as described above.
  • the maximum peak height of crystalline ceria measured by subjecting the ceria-silica composite oxide fine particles (1) to X-ray diffraction for example, the crystallite diameter of the (111) plane is 10 to 50 nm (half value)
  • the total width is 0.86 to 0.17 °, preferably 12 to 30 nm (full width at half maximum is 0.72 to 0.28 °), and 13 to 22 nm (full width at half maximum is 0.66 to 0). .38 °) is more preferable.
  • another crystal plane such as (100) may be the maximum peak.
  • the average crystallite diameter of ceria in the present invention refers to an average crystallite diameter obtained from the full width at half maximum of the crystal peak of the crystal plane where the maximum peak height appears.
  • the average crystallite diameter of the (111) plane of crystalline ceria can be obtained by the method described below.
  • the ceria-silica composite oxide fine particles (1) are pulverized using a mortar, and an X-ray diffraction pattern is obtained using, for example, a conventionally known X-ray diffractometer (for example, RINT1400, manufactured by Rigaku Corporation).
  • a conventionally known X-ray diffractometer for example, RINT1400, manufactured by Rigaku Corporation.
  • the apparent average size of the child particles is preferably 10 to 55 nm, and more preferably 15 to 30 nm.
  • the shape of the child particles may be spherical or rectangular, but is preferably rectangular from the viewpoint of realizing a high polishing rate.
  • the ceria particles on the base particles may be in a monodispersed state or a state in which a plurality of particles are connected. When the size of the child particle ceria is larger than 55 nm, the ceria-silica composite oxide fine particles (1) are condensed to be difficult to disintegrate, and the scratch tends to increase.
  • the size of the child particles is determined by measuring the average particle size of any 50 child particles in a photograph projection view (for example, FIG. 2C described later) enlarged 300,000 times using a transmission electron microscope. It means a value obtained by simple average of these.
  • the silica layer provided on the surface of the mother particle is mainly composed of amorphous silica.
  • the definition of “main component” is as described above.
  • cerium, lanthanum, zirconium or the like is contained in the silica layer, the bond with the mother particles becomes strong.
  • the silica layer of the present invention is particularly preferably a layer containing cerium (cerium-containing silica layer).
  • cerium-containing silica layer there is a process of forming crystalline ceria particles (child particles) by adding a metal salt of cerium.
  • the cerium atoms that have not been formed remain in the layer, and a cerium-containing layer tends to be formed.
  • the firing temperature is increased, cerium diffuses from the silica layer and further ceria crystals grow. In such a case, the strength is not impaired as long as the above process is performed.
  • a silica layer serving as a binder between the mother particles and the child particles is formed on the mother particles, and the ceria particles grown in the silica layer are dispersed.
  • the mother particles and the ceria particles are firmly bonded, and the stability of the ceria-silica composite oxide fine particles (1) is further maintained.
  • the ceria particles are less dropped off, the generation of scratches due to the aggregation of the ceria particles is further suppressed, and the remaining abrasive grains on the substrate are small even though the ceria particles are small. Even if a part of the silica layer is missing, there is no problem in terms of polishing function because the silica layer that binds the ceria particles on the mother particles sufficiently fixes the ceria particles.
  • the image of the child particles appears dark on the surface of the mother particles.
  • a silica layer appears as a relatively thin image.
  • EDS measurement is performed by selectively applying an electron beam to the silica layer portion specified by the transmission electron microscope as described above, the Si atom number% and Ce atom number% of the part are obtained. It can be confirmed that several percent is very high. Specifically, the ratio of Si atom number% to Ce atom number% (Si atom number% / Ce atom number%) is 0.9 or more.
  • the bonding (force) between the child particles (ceria crystal particles) dispersed and grown in the silica layer and the mother particles (silica particles) is promoted in the firing process. Therefore, for example, the ceria-silica composite oxide fine particles (1) obtained by calcination in the step of obtaining the dispersion of the present invention are subjected to wet crushing (operation for breaking the aggregates into original primary particles). Thus, a dispersion of ceria-silica composite oxide fine particles (1) is obtained, but it is considered that the silica layer has an effect of preventing the child particles (ceria crystal particles) from coming off from the mother particles (silica particles). In this case, the local drop of the child particles is not a problem, and the surface of the child particles may not be covered with the silica layer. It is sufficient that the child particles are strong enough not to be separated from the mother particles in the crushing step.
  • the sintered ceria particles are crystallized so that there are few —OH groups on the surface of the particles, and ceria has a potential different from that of silica, a polishing substrate, and a polishing pad.
  • the negative zeta potential decreases and has a reverse positive potential in the weakly acidic region. For this reason, it adheres to the polishing base material and the polishing pad due to the difference in the magnitude of the electric potential and the difference in polarity, and tends to remain on the polishing substrate and the polishing pad.
  • the ceria-silica composite oxide fine particles (1) maintain a negative potential because the potential of the outermost layer is covered with a negative charge resulting from silica, and the abrasive grains remaining on the polishing substrate or polishing pad are not retained. It's hard to get up.
  • the silica layer covers a part or the whole of the particles formed by bonding the child particles on the surface of the mother particles, but the silica layer is not necessarily on the surface of the mother particles. It is not necessary to completely cover the entire particle formed by bonding. That is, the silica layer is present on the outermost surface of the ceria-silica composite oxide fine particles (1), but even if the silica layer is present, the silica layer easily falls off during polishing, and the substrate and the ceria particles Any form that reacts may be used. Furthermore, a part of the silica component may be released to the abrasive dispersion.
  • These silicas are deposited on the surface of ceria particles mainly when the pH is adjusted to 4 to 9 at the time of slurry preparation. These silicas can make the potential of the ceria abrasive negative, and can be expected to improve the polishing rate rather than being a hindrance to polishing.
  • the outermost silica layer is preferably a layer made of easily soluble silica (easily soluble silica layer). Easily soluble silica has an adhesive action between the substrate and abrasive grains, and further promotes the formation of a hydrated layer (fragile layer) on the polishing substrate. As a result, the frictional force during polishing is improved and the polishing rate is increased. Estimated to improve.
  • the mass ratio (M SiO2 : M CeO2 ) between the mother particles and the silica layer and the child particles is preferably 100: 11 to 316, and 100: 30 Is more preferably from 230 to 230, still more preferably from 100: 30 to 150, and particularly preferably from 100: 60 to 120. If the amount of the child particles relative to the mother particles is too small, the mother particles may be bonded to generate coarse particles. In this case, the polishing composition (polishing slurry) of the present invention may cause defects (decrease in surface accuracy such as an increase in scratches) on the surface of the polishing substrate.
  • the amount of the child particles relative to the mother particles is too large, not only is the cost high, but the resource risk increases. Further, the fusion of particles progresses and becomes coarse, which may cause defects (scratches) on the surface of the polishing substrate.
  • the ceria-silica composite oxide fine particles (1) have a silica layer on the surface of the silica fine particles (mother particles), and the crystalline crystalline ceria (child particles) are dispersed in the silica layer. It has a shape.
  • the particle size distribution of the ceria-silica composite oxide fine particles (1) may be “particle-linked” or “monodispersed”, but the contact area with the substrate can be kept high, and the polishing rate
  • the particle connection type is desirable because of its high speed.
  • the particle-linked type is one in which two or more base particles are partially bonded to each other, and the connection is preferably 3 or less. It is considered that at least one (preferably both) of the mother particles are firmly bonded by being welded at their contact points or having a history of solidification due to the presence of ceria.
  • the cerium-containing silica layer is formed on the surface after the mother particles are bonded to each other, the case where the cerium-containing silica layer is formed on the surface of the mother particle and then bonded to the other particles.
  • it is a particle-linked type. Since the contact type can increase the contact area with the substrate, the polishing energy can be efficiently transmitted to the substrate. Therefore, the polishing rate is high.
  • the number ratio of particles having a minor axis / major axis ratio of less than 0.80 (preferably 0.67 or less) measured by image analysis is 45% or more. Is preferred.
  • particles having a minor axis / major axis ratio measured by an image analysis method of less than 0.80 are considered to be of the particle binding type.
  • the shape of the ceria-silica composite oxide fine particles (1) is not particularly limited, and may be particle-coupled particles or single particles (non-coupled particles), and usually a mixture of both. It is.
  • the minor axis / major axis ratio measured by the image analysis method of the ceria-silica composite oxide fine particles (1) is less than 0.80 (preferably 0.67).
  • the number ratio of the following particles is preferably 45% or more (more preferably 51% or more).
  • the minor axis / major axis ratio of the ceria-silica composite oxide fine particles (1) measured by the image analysis method is 0.80.
  • the number ratio of the above particles (preferably 0.9 or more) is preferably 40% or more, and more preferably 51% or more.
  • grain means the particle
  • the single particle means a particle that is not a plurality of particles connected but not agglomerated regardless of the particle morphology.
  • a method for measuring the minor axis / major axis ratio by the image analysis method will be described.
  • Using a transmission electron microscope measure the length of the composite oxide fine particles of the present invention taken with a magnification of 300,000 times (or 500,000 times) with the maximum diameter of the particles as the major axis. Then, the value is taken as the major axis (DL). Further, a point that bisects the major axis on the major axis is determined, two points where a straight line perpendicular to the major axis intersects the outer edge of the particle are obtained, and the distance between the two points is measured to obtain a minor axis (DS). From this, the minor axis / major axis ratio (DS / DL) is obtained. Then, the number ratio (%) of particles having a minor axis / major axis ratio of less than 0.80 or 0.80 or more in any 50 particles observed in the photographic projection diagram is obtained.
  • the ceria-silica composite oxide fine particles (1) are more preferably the above-mentioned particle-linked type, but may contain other shapes, for example, spherical particles.
  • the ceria-silica composite oxide fine particles (1) preferably have a specific surface area of 4 to 100 m 2 / g, and more preferably 20 to 70 m 2 / g.
  • BET specific surface area a method for measuring the specific surface area (BET specific surface area) will be described.
  • a dried sample (0.2 g) is put in a measurement cell, degassed in a nitrogen gas stream at 250 ° C. for 40 minutes, and then the sample is a mixed gas of 30% by volume of nitrogen and 70% by volume of helium. Liquid nitrogen temperature is maintained in a stream of air, and nitrogen is adsorbed to the sample by equilibrium.
  • the temperature of the sample is gradually raised to room temperature while flowing the mixed gas, the amount of nitrogen desorbed during that time is detected, and the specific surface area of the sample is measured using a calibration curve prepared in advance.
  • Such a BET specific surface area measurement method nitrogen adsorption method
  • the specific surface area means a value obtained by such a method unless otherwise specified.
  • the average particle size of the ceria-silica composite oxide fine particles (1) of the present invention is preferably 50 to 350 nm, and more preferably 170 to 260 nm.
  • the average particle diameter of the ceria-silica composite oxide fine particles (1) is in the range of 50 to 350 nm, it is preferable because the polishing rate of the abrasive grains becomes high when applied to the polishing composition.
  • the number of abrasive grains increases when the number of abrasive particles is 50 nm or less, but the size is too small and the polishing power of individual abrasive grains is insufficient, resulting in a slow polishing rate.
  • the average crystallite diameter of ceria is as small as 10 to 50 nm, but ceria is dispersed in the outermost silica layer formed on the core silica mother particles. Therefore, the size of the ceria-silica composite oxide fine particles (1) is the same as that of the crystalline ceria fine particles (fired ceria fine particles), which is a sufficient size suitable for polishing. Furthermore, since the silica layer covering the ceria particles is easily removed by the pressure and frictional force during polishing and ceria is exposed, a high polishing rate is exhibited.
  • the phosphate esterified microfibril cellulose of the present invention is one in which at least a part of the hydroxyl groups of the cellulose unit is phosphate esterified. That is, the phosphate esterified microfibril cellulose of the present invention has a phosphate group.
  • the hydroxyl group is a cellulose-specific hydroxyl group that has not undergone modification such as oxidation, and specifically refers to the hydroxyl group at the C2, C3, or C6 position of the cellulose unit.
  • the phosphoric acid group is formed by bonding directly or via a linking group to the carbon atom at the C2, C3 or C6 position of the cellulose unit. Examples of the linking group include —CH 2 —O— and —CH 2 —O—CH 2 —.
  • the phosphoric acid group (—OP (OH) 3 ) added to the cellulose unit by phosphoric esterification is an ester form in which all or part of the three hydrogens are replaced with an organic group such as an alkyl group or a phenyl group. It may be in the form of a salt such as an ammonium salt.
  • the ammonium present invention, NH 4 + other, NH 4 + 1 or more hydrogen atoms comprises an organic ammonium substituted with organic groups.
  • the C2 and C3 positions of the cellulose unit of the microfibril cellulose before phosphoric acid esterification are “—COH”, but this “—COH” is converted to phosphoric acid ester to “—C—O— P (OH) 3 ”.
  • H + is replaced by NH 4 + to become “—C—O—P (ONH 4 ) 3 ”.
  • “—CH 2 OH” at the C6 position is converted to phosphoric ester to “—CH 2 —OP (OH) 3 ”.
  • the phosphate esterified microfibril cellulose of the present invention is not limited as long as at least a part of the hydroxyl groups of the cellulose unit is phosphate esterified, but the acid group content derived from phosphate groups (the strong acid derived from phosphate groups)
  • the total content of the group and the weak acid group derived from the phosphate group) is preferably 0.1 to 16.8 mmol / g, more preferably 0.4 to 12.0 mmol / g, More preferably, it is from 6 to 8.0 mmol / g.
  • polishing characteristics high polishing rate, low abrasive grain residue, etc.
  • the present inventors believe that during polishing, a part of the strong acid group and a part of the weak acid group are separated and act on the abrasive grains (metal particles), thereby improving the polishing performance. .
  • the content of a strong acid group derived from a phosphate group is preferably 0.1 to 8.4 mmol / g, more preferably 0.2 to 6.0 mmol / g, and 0.3 to 4.0 mmol. More preferably, it is / g.
  • the content of weak acid groups derived from phosphate groups is preferably 0.1 to 8.4 mmol / g, more preferably 0.2 to 6.0 mmol / g, and 0.3 to 4 More preferably, it is 0.0 mmol / g.
  • the phosphate esterified microfibril cellulose of the present invention may have a remaining hydroxyl group and may have other functional groups such as a carboxy group, an aldehyde group, a sulfonic acid group, and a ketone group.
  • the content of the strong acid group derived from the phosphate group is such that the slurry containing the refined phosphate esterified microfibril cellulose after the introduction of the phosphate group is directly subjected to a solid content concentration of 0.2% by mass in ion-exchanged water. It can measure by the process by an ion exchange resin, and the titration using an alkali, after diluting so that it may become.
  • a 1/10 volume of strongly acidic ion exchange resin for example, Amberjet 1024; Organo Corporation, conditioned
  • a value obtained by dividing the amount of sodium hydroxide used when reaching this nick by the solid content in the titration target slurry is defined as the content of strong acid groups derived from phosphate groups.
  • the sodium hydroxide amount used for the titration between the first and second nicks and the value divided by the solid content in the slurry to be measured is the content of weak acid groups derived from phosphate groups.
  • the polishing composition of the present invention using such phosphate esterified microfibril cellulose exhibits a high performance in that it exhibits a high polishing rate and a low-defect polished surface. Moreover, since the dispersibility of microfibril cellulose improves more by phosphoric esterification, a viscosity is low and it is excellent also in filterability.
  • the content of the phosphorylated esterified microfibril cellulose in the polishing composition of the present invention is preferably 100 to 20000 ppm, more preferably 500 to 15000 ppm, still more preferably 1000 to 10,000 ppm, Most preferred is ⁇ 8000 ppm. If it is lower than 100 ppm, the polishing properties may not be improved or may be negligible even if it is improved, and if it is higher than 20000 ppm, the handling property tends to deteriorate due to thickening.
  • each content of Na and K is 100 ppm or less, preferably 50 ppm or less, and more preferably 10 ppm or less.
  • each content of Ag, Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, Zn and Zr is preferably 100 ppm or less, more preferably 50 ppm or less, and 10 ppm or less. Is more preferable.
  • the metal content (content ratio) of the phosphate esterified microfibril cellulose is calculated as the content per phosphate ester microfibril cellulose weight based on the amount of the ignition residue at 200 ° C.
  • the measurement of the content (weight) of each metal such as Na contained in the phosphate esterified microfibril cellulose can be carried out in accordance with the measurement of the base particles of the ceria-silica composite oxide fine particles (1). .
  • the phosphoric esterified microfibril cellulose of the present invention has a number average fiber diameter of 1 to 100 nm, a number average fiber length of 0.01 to 300 ⁇ m, and a ratio of the number average fiber length to the number average fiber diameter (number average fiber It is preferably a fibrous cellulose having a long / number average fiber diameter) of 10 to 3000.
  • the number average fiber diameter is preferably 1 to 100 nm, more preferably 2 to 100 nm, and further preferably 3 to 80 nm from the viewpoint of dispersion stability.
  • Production of phosphate esterified microfibril cellulose having a number average fiber diameter of less than 1 nm is extremely difficult, and even if it can be produced, it may not contribute to improvement of the polishing rate.
  • the number average fiber diameter exceeds 100 nm, the amount of oxidized groups per cellulose molecule decreases, and the interaction with the abrasive grains may be reduced.
  • the maximum fiber diameter of the cellulose fiber is preferably 1000 nm or less, and more preferably 500 nm or less.
  • the number average fiber length (length in the longitudinal direction of the fiber) is preferably 0.01 to 300 ⁇ m, as described above, but more preferably 0.03 to 100 ⁇ m from the viewpoint of dispersion stability, and 0.05 More preferably, it is 50 ⁇ m. That is, if the number average fiber length is less than the above range, the pseudoplastic fluidic rheological effect may be reduced, and conversely, if the number average fiber length exceeds the above range, the cellulose fibers are precipitated, There is a possibility that the functionality due to blending cellulose fibers cannot be expressed.
  • the maximum fiber length of the cellulose fiber is preferably 3000 ⁇ m or less, and more preferably 500 ⁇ m or less.
  • the ratio of the number average fiber length to the number average fiber diameter is preferably 10 to 3000 as described above, but more preferably 10 to 1000 from the viewpoint of polishing characteristics and handling. 10 to 500 are more preferable. If the value of the number average fiber length / number average fiber diameter is less than 10, it is extremely difficult to manufacture, and even if it can be manufactured, the pressing force from the polishing pad cannot be effectively transmitted to the abrasive grains and polishing is performed. The speed may not improve.
  • the amount (mass ratio) of the phosphate esterified microfibril cellulose with respect to the abrasive grains is preferably in the range of 0.001 to 20, preferably 0.005 to 15 in order to show excellent polishing performance. Is more preferable, the range of 0.01 to 10 is further more preferable, and the range of 0.02 to 7.5 is most preferable.
  • the amount of the phosphate esterified microfibril cellulose relative to the abrasive grains is less than 0.001, the amount of the phosphate esterified microfibril cellulose relative to the abrasive grains tends to be insufficient and the polishing rate tends to be difficult to increase.
  • the number average fiber diameter, number average fiber length, maximum fiber length, and maximum fiber diameter of the phosphate esterified microfibril cellulose of the present invention are measured by, for example, the method described in paragraph [0023] of Japanese Patent No. 5744775 (fiber diameter). ) And a method (fiber length) based thereon.
  • the number average fiber diameter can be performed, for example, as follows.
  • An aqueous dispersion of fine cellulose having a solid content of 0.05 to 0.1% by mass was prepared, and the dispersion was cast on a carbon film-coated grid that had been subjected to a hydrophilic treatment, and a transmission electron microscope (TEM). )
  • TEM transmission electron microscope
  • SEM scanning electron microscope
  • observation with an electron microscope image is performed at a magnification of 5,000 times, 10,000 times, or 50,000 times depending on the size of the constituent fibers.
  • phosphate esterified microfibril cellulose used by the said invention demonstrated above is demonstrated.
  • the method for producing such phosphate esterified microfibril cellulose is not particularly limited as long as at least a part of the hydroxyl groups of the cellulose unit can be phosphate esterified, and can be produced by a conventionally known method. .
  • phosphate esterified microfibril cellulose can be produced by allowing a compound having a phosphate group to act on a fiber raw material containing cellulose. At this time, if necessary, urea or a derivative thereof is allowed to coexist. Moreover, it is preferable to carry out the miniaturization process in any process.
  • Examples of the fiber raw material containing cellulose include softwood pulp, hardwood pulp, bagasse pulp, straw pulp, bamboo and the like.
  • Examples of the compound having a phosphate group include phosphoric acid, ammonium phosphate, and alkali metal phosphate (sodium salt, potassium salt, etc.).
  • the ammonium salt, NH 4 + other, NH 4 + 1 or more hydrogen atoms contains organic ammonium salts substituted with organic groups.
  • Examples of the ammonium phosphate salt include triammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium pyrophosphate, ammonium polyphosphate, and the like.
  • examples of the alkali metal phosphate include trisodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, sodium pyrophosphate, sodium polyphosphate, and the like.
  • phosphoric acid and ammonium phosphate are preferable, and ammonium phosphate is particularly preferable because metal contamination can be prevented and it can be suitably used for polishing a semiconductor substrate.
  • ammonium-type phosphate esterified microfibril cellulose in which the hydrogen atom of the phosphate group is replaced with ammonium can also be produced by the following method.
  • a dispersion containing phosphate esterified microfibril cellulose having a phosphate group (—OP (OH) 3 ) is obtained by ion exchange of a dispersion containing phosphate esterified microfibril cellulose using an ion exchange resin. And add ammonia or amine.
  • an ammonium-type phosphate esterified microfibril cellulose in which the hydrogen atom of the phosphate group is converted to ammonium or the like can be obtained.
  • the ion exchange resin is preferably a strongly acidic cation exchange resin or a both ion exchange resin.
  • 100 g of 2.0 mass% phosphoric esterified microfibril cellulose dispersion is subjected to ion exchange using a regenerated cation exchange resin to pH 4 or less, and then pH 8 and Add 5% ammonium hydroxide solution until complete. Thereby, an ammonia type phosphoric esterified microfibril cellulose dispersion can be obtained.
  • the cellulose fiber is refined as necessary (to be converted into microfibril cellulose).
  • cellulose fibers are dispersed (defibrated) in a dispersion medium to be refined.
  • a dispersion medium water or an organic solvent can be used.
  • a high-pressure homogenizer an ultra-high pressure homogenizer, a high-speed shear mixer, an ultrasonic dispersion processing device, a refiner, a beater, or the like can be used.
  • an impurity removal process or a centrifugation process As needed.
  • Impurity removal process In order to enable use in the semiconductor field, it is preferable to remove alkali metals and the like. Moreover, it is preferable to remove an alkaline earth metal and a transition metal like the alkali metal. Specific examples include an ion exchange method and a cleaning method, but the ion exchange method is preferable from the viewpoint of efficiency. What is necessary is just to use what has the ion exchange ability with respect to an alkali metal at least as an ion exchange method, and can use the ion exchange resin which has the ion exchange ability with respect to an alkali metal, an alkaline-earth metal, and a transition metal as needed. In order to efficiently remove alkali metals and alkaline earth metals, strong acid type cation exchange resins are preferred, and in order to efficiently remove transition metals, chelate type ion exchange resins are preferred. Most preferably, these are combined.
  • Centrifugation methods are classified into batch type and continuous type, and continuous centrifuges are equipped with an automatic sediment discharge method, an automatic discharge method for clarified liquid, a rotor equipped with a separation plate, and a rotor. There are various types such as cylindrical and bowl types.
  • the method is not particularly limited as long as sufficient centrifugal acceleration can be applied and the long fiber component and the short fiber component can be sufficiently separated, but in order to separate them almost completely, the batch method is used, and then water is poured. In addition, a method of decanting is desirable.
  • a layer containing cellulose fibers with a short fiber length (a slightly turbid supernatant layer) has a low viscosity
  • a layer containing a cellulose transition with a long fiber length (semi-transparent lower layer) has a very high viscosity. Easy.
  • the pH can be adjusted with an inorganic acid, an organic acid, ammonia, an amine, or the like as necessary.
  • Cellulose fibers are generally neutral, but if they differ greatly from the pH of the abrasive grains, there is a possibility of aggregation of the abrasive grains due to pH shock when mixed with the abrasive grains. Can do.
  • the lower layer cellulose fiber obtained by decantation has a very high viscosity and is difficult to handle, the viscosity can be adjusted by adding ion-exchanged water to reduce the concentration.
  • microfibril cellulose of the present invention for example, a naturally-derived cellulose solid (pulp) raw material is mechanically defibrated and refined (hereinafter sometimes referred to as mechanically refined microfibril cellulose). be able to.
  • mechanically refined microfibril cellulose a naturally-derived cellulose solid (pulp) raw material is mechanically defibrated and refined
  • WMa-100002 manufactured by Sugino Machine Co.
  • CeNF-1 manufactured by Chuetsu Pulp Co., Ltd.
  • Ceraus DF-17 manufactured by Asahi Kasei Co., Ltd., or the like
  • microfibril cellulose of the present invention in addition to the above-mentioned mechanically refined microfibril cellulose, modified microfibrils (hereinafter referred to as oxidatively modified microfibril cellulose) in which at least a part of hydroxyl groups of cellulose units are oxidized to carboxy groups. ) Can be used.
  • oxidatively modified microfibril cellulose usually, at least a part of hydroxyl groups at C2, C3 and C6 positions of the cellulose unit is oxidized to a carboxy group.
  • Such an oxidatively modified microfibril cellulose has a hydroxyl group or an organic group other than a carboxy group, an inorganic functional group such as —SO 3 H having ion exchange ability, or a carbomethyl group, as desired, in addition to a carboxy group. May be.
  • the hydroxyl group means a hydroxyl group specific to cellulose that has not undergone modification such as oxidation, and specifically refers to a hydroxyl group at the C6 position, C3 position or C6 position of the cellulose unit that is not oxidized to a carboxy group.
  • the organic group is formed by bonding directly or via a linking group to a carbon atom at the C2 position, C3 position or C6 position of the cellulose unit that is not oxidized to a carboxy group.
  • a linking group include —CH 2 —O— and —CH 2 —O—CH 2 —.
  • the carboxy group of the modified microfibril cellulose may have a structure in which the hydrogen atom of the carboxy group is substituted with ammonium, and ammonium in the present specification includes NH 4 + , NH 4 + , 1 or 2 It contains organic ammonium in which the above hydrogen atoms are substituted with organic groups.
  • Such a carboxy group (including a salt such as ammonium) may be bonded to a carbon atom via a linking group. Examples of such a linking group include —CH 2 —O— and —CH 2 —O—CH 2 —.
  • the content of microfibril cellulose in the polishing composition of the present invention is preferably 100 to 20000 ppm, more preferably 500 to 15000 ppm, further preferably 1000 to 10,000 ppm, and more preferably 1000 to 8000 ppm. Most preferred. If it is lower than 100 ppm, the polishing properties may not be improved or may be negligible even if it is improved, and if it is higher than 20000 ppm, the handling property tends to deteriorate due to thickening.
  • each content of Na and K is 100 ppm or less, preferably 50 ppm or less, and more preferably 10 ppm or less.
  • each content of Ag, Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, Zn and Zr is preferably 100 ppm or less, more preferably 50 ppm or less, and 10 ppm or less. Is more preferable.
  • the calculation of the metal content (content) of the microfibril cellulose and the measurement of the individual metal content (weight) are the same as those in the above-mentioned phosphorylated microfibril cellulose.
  • ammonium type oxidatively modified microfibril cellulose in which the hydrogen atom of the carboxy group is substituted with ammonium can be preferably exemplified. That is, in the production of ordinary oxidation-modified microfibril cellulose, treatment is carried out using a reagent containing Na or K. Therefore, the hydrogen atom of the carboxy group is substituted with Na or K, and the produced oxidation-modified microfibrils are Although Na or K exceeding 100 ppm is contained, this is converted to ammonium to remove Na and the like.
  • the ammonium, NH 4 + other, NH 4 + 1 or more hydrogen atoms comprises an organic ammonium substituted with organic groups. Thereby, metal contamination can be prevented and the polishing rate can be further improved. Note that other metals can be removed simultaneously with removal of Na and K.
  • oxidatively modified microfibril cellulose of the present invention a part of hydroxyl groups may be converted to aldehyde groups or ketone groups by oxidative modification.
  • Whether the hydroxyl group at the C6 position of each glucose unit in the oxidatively modified microfibril cellulose molecule of the present invention is selectively oxidized can be confirmed by, for example, a 13C-NMR chart. That is, the 62 ppm peak corresponding to the C6 position of the primary hydroxyl group of the glucose unit, which can be confirmed on the 13C-NMR chart of cellulose before oxidation, disappeared after the oxidation reaction, and at the same time, a peak derived from the carboxyl group (178 ppm) ) Appears.
  • the carboxyl group content in the oxidized modified microfibril cellulose of the present invention is preferably 0.5 to 2.8 mmol / g, more preferably 0.8 to 2.8 mmol / g. More preferably, it is 0 to 2.8 mmol / g.
  • the polishing characteristics high polishing rate, low abrasive grain residue, etc.
  • high storage stability, redispersibility and the like can be obtained.
  • the measurement of the content of this carboxy group can be carried out, for example, by the method described in paragraph [0044] of WO2011 / 074301.
  • the number average fiber diameter is 1 to 100 nm
  • the number average fiber length is 0.01 to 300 ⁇ m
  • the ratio of the number average fiber length to the number average fiber diameter (number average fiber length / number average).
  • a fibrous cellulose having a fiber diameter) of 10 to 3000 is preferable.
  • the number average fiber diameter is preferably 1 to 100 nm, more preferably 2 to 100 nm, and further preferably 3 to 80 nm from the viewpoint of dispersion stability.
  • Production of microfibril cellulose having a number average fiber diameter of less than 1 nm is extremely difficult, and even if it can be produced, there is a possibility that it does not contribute to the improvement of the polishing rate.
  • the number average fiber diameter exceeds 100 nm, the amount of oxidized groups per cellulose molecule decreases, and the interaction with the abrasive grains may be reduced.
  • the maximum fiber diameter of the cellulose fiber is preferably 1000 nm or less, and more preferably 500 nm or less.
  • the number average fiber length (length in the longitudinal direction of the fiber) is preferably 0.01 to 300 ⁇ m, as described above, but more preferably 0.03 to 100 ⁇ m from the viewpoint of dispersion stability, and 0.05 More preferably, it is 50 ⁇ m. That is, if the number average fiber length is less than the above range, the pseudoplastic fluid rheological effect may be reduced, and conversely if the number average fiber length exceeds the above range, the cellulose fibers are precipitated, and the cellulose There is a possibility that the functionality due to the blending of fibers cannot be expressed.
  • the maximum fiber length of the cellulose fiber is preferably 3000 ⁇ m or less, and more preferably 500 ⁇ m or less.
  • the ratio of the number average fiber length to the number average fiber diameter is preferably 10 to 3000 as described above, but more preferably 10 to 1000 from the viewpoint of polishing characteristics and handling. 10 to 500 are more preferable. If the value of the number average fiber length / number average fiber diameter is less than 10, it is extremely difficult to manufacture, and even if it can be manufactured, the pressing force from the polishing pad cannot be effectively transmitted to the abrasive grains and polishing is performed. The speed may not improve.
  • the mass ratio of microfibril cellulose to abrasive grains is preferably in the range of 0.001 to 20 for exhibiting excellent polishing performance, and 0.005 to 15 Is more preferable, the range of 0.01 to 10 is further more preferable, and the range of 0.02 to 7.5 is most preferable.
  • the amount of the microfibril cellulose with respect to the abrasive grains is less than 0.001, the amount of the microfibril cellulose with respect to the abrasive grains tends to be insufficient and the polishing rate tends to be difficult to increase.
  • the measurement of the number average fiber diameter, number average fiber length, maximum fiber length, and maximum fiber diameter of the microfibril cellulose of the present invention is the same as that of the phosphate esterified microfibril cellulose of the present invention.
  • the mechanically refined microfibril cellulose of the present invention can be produced, for example, by the following mechanical defibrating process.
  • a defibrator having a large shearing force such as a kneader or a wet pulverizer.
  • the process ends when natural cellulose thickens and the dispersion is determined.
  • the fiber raw material containing cellulose include plant-derived cellulose, and specific examples thereof include softwood pulp, hardwood pulp, bagasse pulp, straw pulp, bamboo, and the like.
  • the method for producing the oxidatively modified microfibril cellulose is not particularly limited as long as it is a method capable of oxidizing at least a part of the hydroxyl group at the C6 position of the cellulose unit, and can be produced by a conventionally known method. Specifically, the method described in JP2009-243014A, the method described in JP2013-181169A, and the like can be exemplified.
  • the oxidation-modified microfibril cellulose used in the present invention can be produced through an oxidation reaction process, a purification process, a refinement process, and the like following the mechanical defibrating process.
  • the co-oxidant is a substance that oxidizes an N-oxyl compound used as an oxidation catalyst.
  • hypohalous acid, halous acid, perhalogen acid, and salts thereof can be used.
  • alkali metal hypohalites such as sodium hypochlorite and sodium hypobromite are preferable.
  • the treatment in the oxidation reaction step is not limited to the above, and ozone, ozone, or oxygen-containing micro / nano bubbles can also be used.
  • N-oxyl compound examples include compounds having a nitroxy radical generally used as an oxidation catalyst.
  • the N-oxyl compound is preferably a water-soluble compound, specifically, piperidine nitroxyoxy radical is preferable, and 2,2,6,6-tetramethylpiperidinooxy radical (TEMPO) is particularly preferable.
  • TEMPO 2,2,6,6-tetramethylpiperidinooxy radical
  • reduction treatment can be performed as necessary.
  • the aldehyde group or ketone group generated in the oxidation reaction treatment is reduced to a hydroxyl group.
  • the cellulose after the oxidation reaction is dispersed in water, the pH is adjusted to about 10, and reduction is performed with various reducing agents such as NaBH 4 .
  • the refined cellulose fiber is dispersed (defibrated) in a dispersion medium to obtain a dispersion of refined cellulose fibers.
  • a dispersion medium water or an organic solvent can be used.
  • a high-pressure homogenizer, an ultra-high pressure homogenizer, a high-speed shear mixer, an ultrasonic dispersion processing device, a refiner, a beater, or the like can be used.
  • the oxidized modified microfibril cellulose used in the present invention can be obtained.
  • the dispersion liquid contains an alkali metal such as Na in terms of the production method, it is not preferable for use in the semiconductor field or the like. By removing alkali metal or the like in this step, it can be used in the semiconductor field. Moreover, it is preferable to remove an alkaline earth metal and a transition metal like the alkali metal.
  • the specific method is the same as the method in the phosphate esterified microfibril cellulose of the said invention.
  • the oxidized modified microfibril cellulose is preferably converted to ammonium-type oxidized modified microfibril cellulose.
  • a dispersion containing oxidatively modified microfibril cellulose is subjected to ion exchange using an ion exchange resin, and then ammonia or amine is added, whereby an ammonium type oxidatively modified microbe in which hydrogen atoms of carboxy groups are converted to ammonium or the like. It can be fibril cellulose.
  • the ion exchange resin a strongly acidic cation exchange resin is preferable.
  • the abrasive grains can be added before or after ion exchange, and can be performed before or after adding ammonia or amine.
  • ammonia or amine is added, and abrasive grains can be added.
  • an abrasive grain can be added and ammonia or an amine can be added.
  • ammonia or an amine can be added after ion-dispersing the dispersion liquid containing oxidation-modified microfibril cellulose and abrasive grains using an ion-exchange resin.
  • the pH can be adjusted with an inorganic acid, an organic acid, ammonia, an amine, or the like as necessary.
  • Cellulose fibers are generally neutral, but if they differ greatly from the pH of the abrasive grains, there is a possibility of aggregation of the abrasive grains due to pH shock when mixed with the abrasive grains. Can do.
  • the lower layer cellulose fiber obtained by decantation has a very high viscosity and is difficult to handle, the viscosity can be adjusted by adding ion-exchanged water to reduce the concentration.
  • phosphoric acid compound of the present invention phosphoric acid (orthophosphoric acid), condensed phosphoric acid, organic phosphoric acid (phosphate ester), and salts thereof can be used.
  • condensed phosphoric acid and salts thereof include chain or cyclic polyphosphoric acid and salts thereof, metaphosphoric acid (glass-like phosphoric acid) and salts thereof, and ultraphosphate.
  • Examples of the cyclic polyphosphoric acid include those having a polymerization degree (n) of 2 to 8, and specific examples thereof include trimetaphosphoric acid and tetrametaphosphoric acid.
  • the organic phosphoric acid has a structure in which all or part of hydrogen atoms of phosphoric acid or condensed phosphoric acid is replaced with an organic group.
  • Examples of the salt include alkali metal salts such as sodium and ammonium salts, but ammonium salts are preferable from the viewpoint of suppressing metal contamination.
  • Examples of the phosphate include a normal salt, a hydrogen salt, and an acidic salt.
  • the addition method (mixing method) of the phosphoric acid compound during the preparation of the polishing slurry of the present invention is not particularly limited as long as the effects of the present invention are exhibited.
  • an abrasive dispersion and a microfibril cellulose dispersion are mixed.
  • the phosphoric acid compound may be mixed later, the abrasive dispersion and the phosphoric acid compound may be mixed in advance and then mixed with the microfibril cellulose dispersion, or the microfibril cellulose dispersion and the phosphoric acid compound may be mixed in advance. Then, it may be mixed with the abrasive dispersion.
  • the phosphoric acid compound may be added without dilution, but it is preferable to dilute and add the phosphoric acid compound solution.
  • the concentration of the phosphoric acid compound in the phosphoric acid compound solution is preferably 0.1 to 30%.
  • the stirring method is not particularly limited as long as it can be uniformly mixed, and can be performed by a conventionally known method. At this time, it is preferable to perform heat treatment simultaneously with stirring.
  • the content of the phosphoric acid compound in the polishing composition is preferably 10 mass ppm to 5 mass%, more preferably 30 mass ppm to 3 mass%, and 50 mass ppm to 1 mass%. Is more preferable. When the content of the phosphoric acid compound is within this range, the effects of the present invention can be effectively exhibited. If the content of the phosphoric acid compound is less than 10 mass ppm, the effect of the phosphoric acid compound may not be sufficiently exerted, and even if the content of the phosphoric acid compound exceeds 5 mass%, an improvement in effect is observed. However, it becomes an excessive amount.
  • the dispersion medium of the present invention preferably contains water as a main component.
  • the definition of “main component” is as described above.
  • water such as pure water, ultrapure water, or ion exchange water can be used.
  • the dispersion medium may contain an organic solvent.
  • organic solvent examples include alcohols such as methanol, ethanol, isopropanol, n-butanol and methyl isocarbinol; ketones such as acetone, 2-butanone, ethyl amyl ketone, diacetone alcohol, isophorone and cyclohexanone; N, N Amides such as dimethylformamide and N, N-dimethylacetamide; ethers such as diethyl ether, isopropyl ether, tetrahydrofuran, 1,4-dioxane, and 3,4-dihydro-2H-pyran; 2-methoxyethanol, 2- Glycol ethers such as ethoxyethanol, 2-butoxyethanol, ethylene glycol dimethyl ether; groups such as 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2-butoxyethyl acetate Cole ether acetates; Esters such as methyl acetate, ethyl,
  • each content of Na, Ag, Al, Ca, Cr, Cu, Fe, K, Mg, Ni, Ti, Zn, Zr, U, and Th is 100 ppm or less per solid content weight. It is preferably 50 ppm or less, more preferably 10 ppm or less.
  • the metal content (content rate) of the polishing composition is calculated based on the amount of residue (solid content) at 200 ° C. of the polishing composition.
  • the measurement of the content (weight) of each metal such as Na contained in the polishing composition can be performed according to the measurement of the base particles of the ceria-silica composite oxide fine particles (1) described above.
  • each metal is 100 ppm or less per weight of solid content, metal contamination can be prevented and it can be suitably used for polishing a semiconductor substrate. Moreover, since the stability of the abrasive grains is further increased, the generation of scratches is further suppressed.
  • the concentration of the solid content contained in the polishing composition of the present invention is preferably in the range of 0.1 to 30% by mass. If this solid content concentration is too low, the polishing rate may decrease. Conversely, even if the solid content concentration is too high, there are few cases where the polishing rate is not improved further in proportion to the concentration, which can be uneconomical.
  • the solid content concentration contained in the polishing composition can be measured by measuring the weight of the burning residue at 200 ° C.
  • the polishing composition of the present invention preferably has a pH of 4-9.
  • the pH is less than 4, ceria in the ceria-based composite fine particles of the present invention may be eluted, and the oxidation-reduction potential changes, so that the polishing rate may be lowered or unstable.
  • the flow potential of (phosphate esterified) microfibril cellulose also tends to decrease.
  • the pH exceeds 9, a pH change is likely to occur due to the elution of silica in the ceria-based composite fine particles.
  • polishing characteristics may change.
  • an alkaline one is used as a pH adjuster.
  • amines such as aqueous ammonia, ammonium carbonate, ethylamine, methylamine, triethylamine, tetramethylamine are used.
  • an acidic one is used as a pH adjuster.
  • organic acids such as hydroxy acids such as acetic acid, lactic acid, citric acid, malic acid, tartaric acid and glyceric acid, and mineral acids such as hydrochloric acid and nitric acid are used.
  • ⁇ PH buffer and ionic strength conditions In the polishing composition of the present invention, 0.0001 to 0.13 mol / L, preferably 0.0003 to 0.1 mol / L of an acid component containing an acetic acid group or a nitric acid group, and 0.003 to 0.13 mol / L L, preferably 0.01 to 0.1 mol / L of an ammonium or amine-containing base component.
  • the polishing characteristics can be stabilized by stabilizing the pH, and at the same time, the polishing rate can be improved by increasing the ionic strength.
  • nitrates, acetates and the like can be used.
  • a compound containing ammonium or amine can be used. Specifically, ammonium, ammonium nitrate containing amine, acetate, and the like, which are monobasic acids such as ammonium nitrate and ammonium acetate, are particularly preferable.
  • the ionic strength of the polishing composition (polishing slurry) of the present invention is preferably 0.007 or more. When the ionic strength of the polishing composition is 0.007 or more, an improvement in the polishing rate is observed.
  • the upper limit of the ionic strength is about 0.1, and more preferably 0.01 to 0.04.
  • the ionic strength of the polishing composition of the present invention means a value calculated from the following formula.
  • J in the formula represents ionic strength.
  • Ci represents the molar concentration of each ion
  • Zi represents the valence of each ion.
  • the molar concentration of each ion is the ion concentration of the substance that dissociates at the pH of the polishing composition of each substance, and thus is calculated using the acid dissociation constant pKa or base dissociation constant pKb of each substance.
  • a salt that dissociates into A ⁇ and B + is added to the polishing composition, it is divided into acid AH and base BOH, and the ion concentrations of A ⁇ and H + , and B + and OH ⁇ are calculated.
  • the acid used for pH adjustment is calculated by dividing AH into A ⁇ and H + and applying the above formula.
  • polishing composition of the present invention a conventionally known polishing accelerator can be used as necessary, although it varies depending on the type of material to be polished. Examples of such include hydrogen peroxide, peracetic acid, urea peroxide and mixtures thereof. When a polishing composition containing such a polishing accelerator such as hydrogen peroxide is used, the polishing rate can be effectively improved when the material to be polished is a metal.
  • polishing accelerators include inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid and hydrofluoric acid, organic acids such as acetic acid, or sodium, potassium, ammonium and amine salts of these acids And the like.
  • inorganic acids such as sulfuric acid, nitric acid, phosphoric acid, oxalic acid and hydrofluoric acid
  • organic acids such as acetic acid, or sodium, potassium, ammonium and amine salts of these acids And the like.
  • a polishing composition containing these polishing accelerators when polishing a material to be polished comprising a composite component, a polishing surface is finally flattened by accelerating the polishing rate for a specific component of the material to be polished. Can be obtained.
  • the content is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.
  • a cationic, anionic, nonionic or amphoteric surfactant or a hydrophilic compound can be added. Both the surfactant and the hydrophilic compound have an action of reducing a contact angle to the surface to be polished and an action of promoting uniform polishing.
  • the surfactant and / or the hydrophilic compound for example, those selected from the following groups can be used.
  • anionic surfactant examples include carboxylate, sulfonate, and sulfate ester salt.
  • carboxylate soap, N-acyl amino acid salt, polyoxyethylene or polyoxypropylene alkyl ether carboxylate, acylation Peptide; alkyl sulfonate, alkyl benzene and alkyl naphthalene sulfonate, naphthalene sulfonate, sulfosuccinate, ⁇ -olefin sulfonate, N-acyl sulfonate; sulfate ester as sulfate ester Mention may be made of oils, alkyl sulfates, alkyl ether sulfates, polyoxyethylene or polyoxypropylene alkyl allyl ether sulfates, alkyl amide sulfates.
  • cationic surfactant aliphatic amine salt, aliphatic quaternary ammonium salt, benzalkonium chloride salt, benzethonium chloride, pyridinium salt, imidazolinium salt; as amphoteric surfactant, carboxybetaine type, sulfobetaine type, Mention may be made of aminocarboxylates, imidazolinium betaines, lecithins, alkylamine oxides.
  • Nonionic surfactants include ether type, ether ester type, ester type and nitrogen-containing type.
  • Ether type includes polyoxyethylene alkyl and alkylphenyl ether, alkylallyl formaldehyde condensed polyoxyethylene ether, polyoxyethylene poly Examples include oxypropylene block polymer, polyoxyethylene polyoxypropylene alkyl ether, ether ester type, glycerin ester polyoxyethylene ether, sorbitan ester polyoxyethylene ether, sorbitol ester polyoxyethylene ether, ester type, Polyethylene glycol fatty acid ester, glycerin ester, polyglycerin ester, sorbitan ester, propylene glycol ester Le, sucrose esters, nitrogen-containing type, fatty acid alkanolamides, polyoxyethylene fatty acid amides, polyoxyethylene alkyl amide, and the like.
  • a fluorine-type surfactant etc. are mentioned.
  • an anionic surfactant or a nonionic surfactant is preferable, and as the salt, ammonium salt, potassium salt, sodium salt and the like can be mentioned, and ammonium salt and potassium salt are particularly preferable.
  • esters such as glycerin ester, sorbitan ester and alanine ethyl ester; polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene glycol alkyl ether, polyethylene glycol alkenyl ether, alkyl Polyethylene glycol, alkyl polyethylene glycol alkyl ether, alkyl polyethylene glycol alkenyl ether, alkenyl polyethylene glycol, alkenyl polyethylene glycol alkyl ether, alkenyl polyethylene glycol alkenyl ether, polypropylene glycol alkyl ether, polypropylene glycol alkenyl ether, alkyl polypropylene Ethers such as recall, alkyl polypropylene glycol alkyl ether, alkyl polypropylene glycol alkenyl ether, alkenyl polypropylene glycol; polysaccharides such as alginic acid, pectic acid, alkyl alkyl ether,
  • an acid or its ammonium salt surfactant is used. It is desirable to do.
  • the total content is preferably 0.001 to 10 g in 1 L of the polishing slurry, It is more preferably from 5 to 5 g, particularly preferably from 0.1 to 3 g.
  • the content of the surfactant and / or the hydrophilic compound is preferably 0.001 g or more in 1 L of the polishing slurry, and is preferably 10 g or less from the viewpoint of preventing the polishing rate from being lowered.
  • the heterocyclic compound is formed for the purpose of suppressing the erosion of the substrate to be polished by forming a passive layer or a dissolution inhibiting layer on the metal. May be included.
  • the “heterocyclic compound” is a compound having a heterocyclic ring containing one or more heteroatoms.
  • a hetero atom means an atom other than a carbon atom or a hydrogen atom.
  • a heterocycle means a cyclic compound having at least one heteroatom.
  • a heteroatom means only those atoms that form part of a heterocyclic ring system, either external to the ring system, separated from the ring system by at least one non-conjugated single bond, Atoms that are part of a further substituent of are not meant.
  • Preferred examples of the hetero atom include, but are not limited to, a nitrogen atom, a sulfur atom, an oxygen atom, a selenium atom, a tellurium atom, a phosphorus atom, a silicon atom, and a boron atom.
  • imidazole, benzotriazole, benzothiazole, tetrazole, and the like can be used.
  • 1,2,3,4-tetrazole, 5-amino-1,2,3,4-tetrazole, 5-methyl-1,2,3,4-tetrazole, 1,2,3- Triazole, 4-amino-1,2,3-triazole, 4,5-diamino-1,2,3-triazole, 1,2,4-triazole, 3-amino1,2,4-triazole, 3,5 -Diamino-1,2,4-triazole and the like can be mentioned, but are not limited thereto.
  • the content of the heterocyclic compound in the polishing composition of the present invention is preferably 0.001 to 1.0% by mass, more preferably 0.001 to 0.7% by mass. More preferably, the content is 0.002 to 0.4% by mass.
  • the polishing composition of the present invention has improved polishing performance, the generation of fungi such as algae and spiders over time in the polishing composition, and the prevention of organic contamination to the substrate due to the growth-inhibiting effect, and the manufacturing process or product
  • nanobubbles may be added for the purpose of improving the stability of appearance, stability of concentration, or improvement of filterability, stability such as algicide by using nanobubble aqueous solution, bactericidal effect, etc. it can.
  • nanobubbles nanobubbles having an average bubble diameter in the range of 50 to 500 nm are preferably used.
  • the type of gas contained in the nanobubble is not particularly limited as long as the effect of crushing the microgel derived from the composition component can be exhibited by bursting of the nanobubble, but usually air, N 2 , H 2 and O 2 are preferably substantially composed of at least one selected from the group consisting of H 2 and O 2 .
  • the gas contained in the nanobubbles is particularly preferably a non-oxidizing gas, and examples of such gas include N 2 and H 2 .
  • the method of adding nanobubbles to the polishing composition is not particularly limited, and for example, a method of adding and mixing an aqueous solution containing nanobubbles while maintaining the polishing composition at 5 to 80 ° C. is used.
  • the nanobubble aqueous solution a nanobubble aqueous solution containing 10 5 / mL or more of nanobubbles having an average bubble diameter in the range of 50 to 500 nm is preferably used.
  • Preparation Example 1-1 Preparation of ceria-based composite fine particles ⁇ Preparation of silica sol (average particle diameter 63 nm) >> Ethanol 12,090 g and normal ethyl silicate 6,363.9 g were mixed to obtain a mixed solution a1. Next, 6,120 g of ultrapure water and 444.9 g of 29% ammonia water were mixed to obtain a mixed solution b1. Next, 192.9 g of ultrapure water and 444.9 g of ethanol were mixed and used as bedding water. Then, the stirring water was adjusted to 75 ° C. while stirring, and the mixed solution a1 and the mixed solution b1 were simultaneously added so that the addition was completed in 10 hours each.
  • the liquid temperature was kept at 75 ° C. for 3 hours and ripened, and then the solid content concentration was adjusted, and the SiO 2 solid content concentration was 19% by mass, and the average particle size was 63 nm measured by the image analysis method. 9,646.3 g of silica sol was obtained.
  • the liquid temperature was kept at 65 ° C. for 3 hours for aging, and then the solid content concentration (SiO 2 solid content concentration) was adjusted to 19% by mass to obtain 3,600 g of high-purity silica sol. .
  • the particles contained in this high-purity silica sol had an average particle size of 113 nm as measured by image analysis. Further, the content of alkali, alkaline earth metal, etc., U, Th, Cl, NO 3 , SO 4 , and F by atomic absorption spectroscopic analysis or ICP measurement was 1 ppm or less.
  • a cation exchange resin (SK-1BH, manufactured by Mitsubishi Chemical Corporation) was gradually added to 1,053 g of this high-purity silica sol and stirred for 30 minutes to separate the resin.
  • the pH at this time was 5.1.
  • Ultrapure water was added to the obtained silica sol to obtain 6,000 g of A liquid having a SiO 2 solid content concentration of 3 mass%.
  • the temperature of the liquid A (6,000 g) was raised to 50 ° C., and while vigorously stirring, the liquid B (8,453 g, 100 mass parts of SiO 2) was equivalent to 117.4 mass of CeO 2. Was added over 18 hours. During this time, the liquid temperature was maintained at 50 ° C., and 3% ammonia water was added as necessary to maintain pH 7.85. And when addition of B liquid was complete
  • the fired powder pulverized dispersion was treated with a centrifuge (model number “CR21G” manufactured by Hitachi Koki Co., Ltd.) at 1700 G for 102 seconds, and the light liquid was recovered.
  • the obtained light liquid is concentrated with a rotary evaporator, then diluted with ion-exchanged water to adjust the concentration to 20%, and further filtered with a 3 ⁇ m filter (CCP-3-D1B manufactured by Advantech Toyo Co., Ltd.).
  • a system composite fine particle dispersion was obtained.
  • the solid content concentration of the obtained ceria composite fine particles was 20%.
  • the ceria composite fine particles contained in the ceria composite fine particle dispersion obtained in Preparation Example 1-1 were observed using SEM and TEM.
  • An SEM image and a TEM image (100,000 times) are shown in FIGS.
  • a transmission electron microscope image (300,000 times) obtained by measuring the particle diameter of the child particles is shown in FIG.
  • FIG. 3 shows an X-ray diffraction pattern of the ceria-based composite fine particles contained in the ceria-based composite fine particle dispersion obtained in Preparation Example 1-1.
  • a cation exchange resin regenerated with sulfuric acid Diaion SK-1B, manufactured by Mitsubishi Chemical Corporation
  • solution A a microfibril cellulose diluted solution having a solid content concentration of 0.21% by mass.
  • 0.53 g of triammonium phosphate trihydrate Kanto Chemical Co., Ltd., deer grade 1 purity 95% by mass was added, and stirring was continued for 10 minutes. The temperature was raised to ° C and kept at 95 ° C for 1 hour.
  • the mixture was allowed to cool to room temperature, and then concentrated with a rotary evaporator to obtain a 2.0% by mass phosphated microfibril cellulose dispersion.
  • concentration of phosphate esterified microfibril cellulose was calculated
  • the amount of phosphate group of phosphate esterified microfibril cellulose was determined by the following procedure. 2.0 g of phosphoric esterified microfibril cellulose dispersion 11 g and 189 g of ion-exchanged water were mixed to prepare 200 g of a solution having a solid content concentration of 0.11 mass%. Next, 13 g of a regenerated strong acidic cation exchange resin (Diaion SK1BH manufactured by Mitsubishi Chemical Corporation) was added, and stirring was continued until the pH became stable. The pH at this time was 3.4. A cation exchange resin was separated from this solution to obtain a phosphate group measurement solution having a solid content concentration of 0.1% by mass.
  • a regenerated strong acidic cation exchange resin Diaion SK1BH manufactured by Mitsubishi Chemical Corporation
  • Phosphoric acid group-derived strong acid group content V 1 (ml) ⁇ 0.05 / cellulose fiber (g)
  • Weak acid group content derived from phosphate groups V 2 (ml) ⁇ 0.05 / cellulose fiber (g)
  • Table 1 shows the physical properties and impurity content of phosphate esterified microfibril cellulose.
  • the major axis in Table 1 represents the number average fiber length
  • the minor axis represents the number average fiber diameter
  • the major axis / minor axis ratio is the ratio of the number average fiber length to the number average fiber diameter (number average fiber length). / Number average fiber diameter).
  • ⁇ Preparation Example 1-3> Preparation of calcined ceria particles Cerium carbonate was calcined for 2 hours using a muffle furnace at 710 ° C. to obtain a powdery calcined product. Next, 100 g of the fired powder and 300 g of ion-exchanged water were put into a 1 L beaker with a handle, and ultrasonic waves were irradiated for 10 minutes in an ultrasonic bath while stirring. Next, wet crushing (a batch type tabletop sand mill manufactured by Campe Co., Ltd.) was performed for 30 minutes using quartz beads having a diameter of 0.25 mm (manufactured by Daiken Chemical Industry Co., Ltd.).
  • the beads After crushing, the beads were separated through 44-mesh metal mesh while being pushed with ion-exchanged water to obtain a ceria fine particle precursor dispersion.
  • the solid content concentration of the obtained dispersion was 5.6% by mass.
  • the obtained ceria fine particle precursor dispersion was centrifuged for 102 seconds at a relative centrifugal acceleration of 1700 G with a centrifugal separator (manufactured by Hitachi Koki Co., Ltd., model number “CR21G”) to remove sediment components, The solution after removal was concentrated to 20% by mass with a rotary evaporator to obtain a ceria fine particle dispersion.
  • Example 1-1 Ion exchange water was added to the phosphate esterified microfibril cellulose obtained in Preparation Example 1-2 to adjust to 0.25% by mass.
  • ion-exchanged water was added to 4.5 g (dry 0.9 g) of the ceria-based composite fine particle dispersion obtained in Preparation Example 1-1, and 0.25% phosphate ester was further stirred.
  • Microfibril cellulose (1) 120 g, dry 0.30 g was added.
  • 3% nitric acid was added to adjust the pH to 5.0, and finally, ion-exchanged water was added and stirred for 10 minutes, so that 150 g of a polishing slurry having a pH of 5.0 and an abrasive concentration of 0.6% by mass was obtained.
  • concentration of phosphate esterified microfibril cellulose (1) was 2000 ppm.
  • a polishing test was performed using the obtained slurry. Specifically, the polishing test was performed as follows (the same applies to the following examples and comparative examples).
  • polishing test method ⁇ Polishing of SiO 2 film>
  • a SiO 2 insulating film (thickness 1 ⁇ m) substrate prepared by a thermal oxidation method was prepared.
  • the substrate to be polished is set in a polishing apparatus (NF300, manufactured by Nano Factor Co., Ltd.), and a polishing pad (“IC-1000 / SUBA400 concentric type” manufactured by Nitta Haas) is used. Polishing was performed by supplying the polishing slurry at a rotational speed of 90 rpm by a dropping method at a rate of 50 ml / min for 1 minute.
  • rate was calculated by calculating
  • smoothness (surface roughness Ra) of the surface of the polishing substrate was measured using an atomic force microscope (AFM, manufactured by Hitachi High-Tech Science Co., Ltd.). Since smoothness and surface roughness are generally proportional, Table 4 lists the surface roughness.
  • the observation of the polishing flaw was performed by observing the surface of the insulating film using an optical microscope.
  • a substrate for aluminum hard disk is set in a polishing apparatus (NF300, manufactured by Nano Factor Co., Ltd.), and a polishing pad (“Polytex ⁇ 12” manufactured by Nitta Haas Co., Ltd.) is used, and polishing slurry is applied at a substrate load of 0.05 MPa and a table rotation speed of 30 rpm.
  • a polishing apparatus NF300, manufactured by Nano Factor Co., Ltd.
  • a polishing pad (“Polytex ⁇ 12” manufactured by Nitta Haas Co., Ltd.) is used, and polishing slurry is applied at a substrate load of 0.05 MPa and a table rotation speed of 30 rpm.
  • Polishing is performed by supplying at a rate of 20 ml / min for 5 minutes by a dripping method, using an ultra-fine defect / visualization macro device (manufactured by VISION PSYTEC, product name: Micro-Max), and observing the entire surface with Zoom 15; The number of scratches (linear traces) present on the polished substrate surface corresponding to 65.97 cm 2 was counted and totaled and evaluated according to the following criteria. Number of linear marks Evaluation Less than 50 “Very few” 50 to less than 80 80 or more "Many"
  • Example 1-2 Ion exchange water was added to the phosphate esterified microfibril cellulose obtained in Preparation Example 1-2 to adjust to 0.5% by mass. Next, 13.5 g of ion-exchanged water was added to 4.5 g (dry 0.9 g) of the ceria-based composite fine particle dispersion obtained in Preparation Example 1-1, and 0.5 mass% phosphate ester was further stirred. Microfibril cellulose (1) 120 g (dry 0.6 g) was added.
  • Example 1-1 the same procedure as in Example 1-1 was performed, except that the ceria fine particle dispersion obtained in Preparation Example 1-3 was used in place of the ceria-based fine particles as the abrasive grains in the polishing slurry. It was.
  • Example 1-1 ⁇ Comparative Example 1-3> In Example 1-1, except that microfibril cellulose not subjected to phosphorylation treatment (WMa-100002 manufactured by Sugino Machine Co., Ltd.) was used instead of phosphate esterified microfibril cellulose, Example 1- 1 was performed.
  • phosphorylation treatment WMa-100002 manufactured by Sugino Machine Co., Ltd.
  • Comparative Example 1-4 In Comparative Example 1-3, the same procedure as in Comparative Example 1-3 was performed, except that the ceria fine particles obtained in Preparation Example 1-3 were used in place of the ceria-based fine particles as the abrasive grains in the polishing slurry.
  • Comparative Example 1-6 a polishing slurry was prepared using microfibril cellulose (WMa-1002 manufactured by Sugino Machine Co., Ltd.) instead of using phosphate esterified microfibril cellulose. Carried out.
  • microfibril cellulose Wa-1002 manufactured by Sugino Machine Co., Ltd.
  • Table 2 shows the average particle size, properties, and impurity content of the silica base particles of the ceria composite fine particles produced above.
  • Table 3 shows the ceria-based composite fine particles, the child particles, and the production conditions. Further, Table 4 shows the composition, pH, impurity content, abrasive concentration and polishing evaluation results of the slurry used in the polishing test.
  • the polishing compositions (Examples 1-1 to 1-3) of the present invention using phosphate esterified microfibril cellulose have less impurity, improve the polishing rate, and reduce scratches. It can also be seen that the smoothness (surface roughness) is also good.
  • ⁇ Preparation example 2-1> Preparation of ceria-based composite fine particles The same procedure as in ⁇ Preparation example 1-1> was performed.
  • a cation exchange resin regenerated with sulfuric acid Diaion SK
  • Table 5 shows the physical properties and impure content of high purity microfibril cellulose.
  • the major axis in Table 5 represents the number average fiber length
  • the minor axis represents the number average fiber diameter
  • the major axis / minor axis ratio is the ratio of the number average fiber length to the number average fiber diameter (number average fiber length). / Number average fiber diameter).
  • Preparation Example 2-3 Preparation of calcined ceria particles The same procedure as in Preparation Example 1-3 was performed.
  • Example 2-1 Ion exchange water was added to the high purity microfibril cellulose obtained in Preparation Example 2-2 to adjust to 0.25% by mass. Next, ion exchange water was added to deer first grade triammonium phosphate trihydrate manufactured by Kanto Chemical Co., Ltd. to prepare a 10 mass% triammonium phosphate aqueous solution.
  • ion-exchanged water was added to 4.5 g (dry 0.9 g) of the ceria-based composite fine particle dispersion obtained in Preparation Example 2-1, and the mixture was further stirred to obtain a 0.25% high-purity micro-particle.
  • 120 g (dry 0.30 g) of fibril cellulose was added, and 0.6 g of a 10% by mass aqueous triammonium phosphate solution was further added.
  • 3% nitric acid was added, finally ion-exchanged water was added, and the mixture was stirred for 10 minutes to obtain 150 g of a polishing slurry having a pH of 5.0 and an abrasive concentration of 0.6% by mass.
  • the concentration of high purity microfibril cellulose was 2000 ppm, and the concentration of triammonium phosphate was 400 ppm.
  • the content of Na and K per solid weight of the obtained polishing slurry was 1 ppm or less.
  • the content of Ag, Al, Ca, Cr, Cu, Fe, Mg, Ni, Ti, Zn, and Zr per solid weight of the polishing slurry was 1 ppm or less.
  • a polishing test was performed using the resulting slurry.
  • Example 2-2 Ion exchange water was added to the high purity microfibril cellulose obtained in Preparation Example 2-2 to adjust to 0.5% by mass. Next, 13.5 g of ion-exchanged water was added to 4.5 g (dry 0.9 g) of the ceria-based composite fine particle dispersion obtained in Preparation Example 2-1, and the mixture was further stirred to 0.5 mass% of high-purity microparticles. 120 g (dry 0.6 g) of fibril cellulose was added.
  • Example 2-1 1.2 g of 10% by mass triammonium phosphate obtained in the same manner as in Example 2-1 was added, then 3% nitric acid was added, and finally ion-exchanged water was added to adjust the pH to 5.0.
  • the concentration of high purity microfibril cellulose in the polishing slurry was 4000 ppm, and the concentration of triammonium phosphate was 800 ppm.
  • the same analysis as in Example 2-1 was performed, and a polishing test was similarly performed.
  • Example 2-3 In Example 2-1, the same procedure as in Example 2-1 was performed, except that the ceria fine particle dispersion obtained in Preparation Example 2-3 was used in place of the ceria composite fine particles as the abrasive grains in the polishing slurry. It was.
  • Example 2-1 the same procedure as in Example 2-1, except that triammonium phosphate was not added, and microfibril cellulose (WMa-10002 manufactured by Sugino Machine Co.) was used instead of high-purity microfibril cellulose. Went to.
  • Comparative Example 2-3 the same procedure as in Comparative Example 2-3 was performed, except that the ceria fine particles obtained in Preparation Example 2-3 were used in place of the ceria-based fine particles as the abrasive grains in the polishing slurry.
  • Comparative Example 2-5 was carried out in the same manner as Comparative Example 2-5 except that triammonium phosphate was not added.
  • Table 6 shows the average particle diameter, properties, and impurity content of the silica base particles of the ceria composite fine particles produced above.
  • Table 7 shows the ceria-based composite fine particles, the child particles, and the production conditions.
  • Table 8 shows the composition, pH, impurity content, abrasive concentration, and polishing evaluation results of the slurry used in the polishing test.
  • the polishing compositions of the present invention using high-purity microfibril cellulose have less impurities, improve the polishing rate, reduce scratches, and It can be seen that the smoothness (surface roughness) is also good.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Materials Engineering (AREA)
  • Silicon Compounds (AREA)
  • Mechanical Treatment Of Semiconductor (AREA)

Abstract

La présente invention a pour objet de fournir une composition de polissage qui peut polir un substrat sur lequel est formé un revêtement de silice ou similaire à grande vitesse en augmentant les effets de frottement mécanique à l'aide de grains abrasifs qui ne produisent pas de défauts, qui permet d'obtenir simultanément une précision de surface élevée telle qu'un faible rayage et qui peut également être utilisée de façon appropriée pour un substrat semi-conducteur. À cet effet, l'invention porte sur une composition de polissage qui est caractérisée par l'inclusion d'un milieu de dispersion, de grains abrasifs et d'au moins un type de composant choisi parmi I) une cellulose microfibrillaire estérifiée par un phosphate et II) une cellulose microfibrillaire et un composé phosphate.
PCT/JP2019/015060 2018-04-11 2019-04-05 Composition de polissage Ceased WO2019198622A1 (fr)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022103985A (ja) * 2020-12-28 2022-07-08 日揮触媒化成株式会社 セリア系複合微粒子分散液、その製造方法及びセリア系複合微粒子分散液を含む研磨用砥粒分散液
TWI820399B (zh) * 2021-02-26 2023-11-01 國立臺灣科技大學 晶圓加工方法及晶圓加工系統

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049031A (ja) * 1999-06-04 2001-02-20 Asahi Chem Ind Co Ltd 無機粒子分散組成物
WO2002031079A1 (fr) * 2000-10-06 2002-04-18 Mitsui Mining & Smelting Co.,Ltd. Matière abrasive
JP2009065041A (ja) * 2007-09-07 2009-03-26 Asahi Kasei Chemicals Corp 微細繊維状セルロース及び／又はその複合体を含む化学機械研磨用組成物
WO2012090510A1 (fr) * 2010-12-29 2012-07-05 Hoya株式会社 Procédé de fabrication pour substrat en verre pour disque magnétique, et procédé de fabrication pour disque magnétique
JP2019026822A (ja) * 2017-01-16 2019-02-21 日揮触媒化成株式会社 研磨組成物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001049031A (ja) * 1999-06-04 2001-02-20 Asahi Chem Ind Co Ltd 無機粒子分散組成物
WO2002031079A1 (fr) * 2000-10-06 2002-04-18 Mitsui Mining & Smelting Co.,Ltd. Matière abrasive
JP2009065041A (ja) * 2007-09-07 2009-03-26 Asahi Kasei Chemicals Corp 微細繊維状セルロース及び／又はその複合体を含む化学機械研磨用組成物
WO2012090510A1 (fr) * 2010-12-29 2012-07-05 Hoya株式会社 Procédé de fabrication pour substrat en verre pour disque magnétique, et procédé de fabrication pour disque magnétique
JP2019026822A (ja) * 2017-01-16 2019-02-21 日揮触媒化成株式会社 研磨組成物

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2022103985A (ja) * 2020-12-28 2022-07-08 日揮触媒化成株式会社 セリア系複合微粒子分散液、その製造方法及びセリア系複合微粒子分散液を含む研磨用砥粒分散液
JP7549528B2 (ja) 2020-12-28 2024-09-11 日揮触媒化成株式会社 セリア系複合微粒子分散液、その製造方法及びセリア系複合微粒子分散液を含む研磨用砥粒分散液
TWI820399B (zh) * 2021-02-26 2023-11-01 國立臺灣科技大學 晶圓加工方法及晶圓加工系統

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